B.P. Jacobs et al. / Journal of Organometallic Chemistry xxx (2017) 1e8
7
Celite. The THF was removed, and the residue was washed with
hexanes (3 ꢃ 10 mL), and the red suspension filtered in hexanes to
afford a red powder (275 mg, 73%). Crystals suitable for X-ray
diffraction were obtained via letting a concentrated C6D6 solution
separate 25 mL flask. The solvent was removed, and 10 mL pentane
was added via vacuum transfer. The pentane mixture was cooled
to ꢀ78 ꢁC for 15 min, and filtered to afford a yellow powder
(230 mg, 55%). 1H NMR (C6D6):
d 0.87 (18H, d, 5 Hz), 1.40 (6H, t, 3
stand for 12 h at 23 ꢁC. 1H NMR (C6D6):
d
1.41 (4H, br s), 1.64e1.70
hz), 1.43 (6H, t, 2 Hz), 2.00 (2H, m), 2.39 (2H, dq, 15, 7 Hz), 7.03 (2H,
t, 7 Hz), 7.10 (2H, t, 7 Hz), 7.23 (2H, dt, 7, 3 Hz), 7.43 (2H, d, 7 Hz). 13
NMR (C6D6): 17.30 (t, 10 Hz), 20.10, 23.84 (“t”, 8 Hz), 34.78 (t,
16 Hz), 123.18, 125.38, 128.59, 128.96 (t, 6 Hz), 145.40, 163.57 (t,
24 Hz). 31P NMR (C6D6):
18.79 (t, 33 Hz), 53.50 (t, 33 Hz). Anal. for
24H42FeP4 (calc.) C 56.48, H 8.30; (found) C 56.46, H 8.32.
(24H, br “s”), 2.42 (1H, s), 3.44 (1H, s), 3.55 (4H, br s), 6.76 (2H, br s),
6.79e6.94 (14H, m), 7.00 (4H, m), 7.03e7.05 (10H, m), 7.06 (1H, t,
7 Hz), 7.10 (1H, dd, 4 7 and 4 Hz), 7.14 (1H, br s), 7.23e7.29 (3H, m),
C
d
7.37 (5H, m), 7.94 (4H, m). 31P NMR (C6D6):
(2P).
d
ꢀ13.37 (1P), ꢀ15.71
d
C
5.2.5. (Me2IPr)Fe(CH2C6H4-o-NMe2)2 (3-C,N)
5.3. NMR tube and small scale reactions
To
a 25-mL flask charged with (Me2IPr)FeCl2 (218 mg,
0.710 mmol) and LiCH2C6H4-o-NMe2 (200 mg, 1.42 mmol) was
added 10 mL ether via vacuum transfer at ꢀ78 ꢁC. The yellow
suspension did not change color, and was allowed to slowly warm
with stirring for 17 h. At 23 ꢁC, the solution turned brown-orange
with colorless precipitate, and was filtered. The ether solution
was concentrated and cooled to ꢀ78 ꢁC for 15 min. The solution was
filtered, and concentrated to afford yellow microcrystals (202 mg,
57%), whose purity was assessed at ~97% based on NMR spectros-
Flame-dried NMR tubes, sealed to 14/20 ground glass joints,
were charged with metal reagent (typically ~10 mg, 10ꢀ2 mmol)
and other solid substrates in the dry box, attached to needle valves,
and moved to the vacuum line. The tubes were degassed, and after
vacuum transfer of deuterated solvent, were flame sealed with a
torch. In the case of small scale reactions, 10 mL or 25 mL flasks
were loaded with reagents in the glovebox, and appended to needle
valves. Solvents were added via vacuum transfer, and upon
conclusion of the reaction, the volatiles were removed and the
assembly transferred to the glovebox for analysis. Consult the text
for particular reactions.
copy. 1H NMR (C6D6):
d
ꢀ27.95 (2H), ꢀ13.69 (2H), ꢀ9.21 (6H), 16.14
(12H), 25.57 (2H), 38.88 (2H), 40.45 (12H). meff (Evans) ¼ 5.2 mB
.
Anal. for C29H44FeN4 (calc.) C 69.04, H 8.79, N 11.10; (found) C 68.98,
H 8.81, N 11.01.
5.4. Single crystal X-Ray diffraction study
5.2.6. [(Me2IPr)2Fe](m-k-C,P-CH2PMe2)2[Fe(k-C,P-CH2PMe2)2] (4)
To 25 mL flask charged with (Me2IPr)FeCl2 (277 mg,
a
5.4.1. Crystal data for 1
0.902 mmol) and LiCH2PMe2 (148 mg, 1.80 mmol) was added via
vacuum transfer 15 mL ether at ꢀ78 ꢁC, resulting in an orange so-
lution. The solution was allowed to warm slowly with stirring for
40 h. The volatiles were removed, and the orange residue taken up
in 10 mL THF and filtered through dried Celite. Removal of the
solvent, followed with washing the residue with hexanes
(3 ꢃ 10 mL), resulted in an orange powder (285 mg, 82%). Crystals
suitable for X-ray diffraction were obtained via layering a concen-
trated THF solution of 4 with pentane (1:3) and letting the solution
C
36H48N4Fe2, M ¼ 648.48, monoclinic, P21/c, a ¼ 9.8560 (7),
b ¼ 14.5425 (11), c ¼ 12.4977 (9) Å,
b
¼ 111.796 (4)ꢁ, V ¼ 1663 (9) Å3,
D ¼ 1.295 g/cm3, T ¼ 223 (2) K,
l
¼ 0.71073 Å, Z ¼ 2, Rint ¼ 0.0357,
16496 reflections, 3685 independent, R1(all data)
wR2 ¼ 0.0994, GOF ¼ 1.013, CCDC-1529975.
¼
0.0480,
5.4.2. Crystal data for 2
C
84H95N4LiP3Fe, M ¼ 1316.33, triclinic, P-1, a ¼ 13.2061 (6),
b ¼ 14.0219 (6), c ¼ 20.7264 (10) Å,
a
¼ 98.823 (2)ꢁ,
b
¼ 101.703 (2)ꢁ,
stand at 23 ꢁC for 12 h 1H NMR (C6D6):
(6H), 5.42 (12H), 17.24 (6H), 27.15 (4H). meff (Evans) ¼ 5.0(3) mB
d 0.78 (2H), 2.31 (6H), 2.65
g
l
¼ 93.670 (2)ꢁ,V ¼ 3695.8 (3) Å3, D ¼ 1.183 g/cm3, T ¼ 223 (2) K,
.
¼ 0.71073 Å, Z ¼ 2, Rint ¼ 0.0468, 66905 reflections, 15088 in-
dependent, R1(all data) ¼ 0.0623, wR2 ¼ 0.0988, GOF ¼ 1.025,
5.2.7. (PMe3)2Fe(k-C,P-CH2PMe2)2 (5)
CCDC-1529976.
To 25-mL flask charged with FeCl2(PMe3)2 (340 mg,
a
1.22 mmol) and LiCH2PMe2 (200 mg, 2.44 mmol) was added 15 mL
ether via vacuum transfer at ꢀ78 ꢁC, resulting in a dark-brown
solution. The solution was allowed to slowly warm to 23 ꢁC for
2 d. The brown solution was filtered and the volatiles removed,
producing a dark-brown residue. Attempts at trying to crystallize
the compound from hexanes failed, as no solid precipitate was
observed, regardless of concentration or temperature. The volatiles
were evaporated, and the sticky brown solid was harvested
5.4.3. Crystal data for 4
C
34H72N4P4Fe2, M ¼ 772.53, monoclinic, P21/n, a ¼ 13.1748 (6),
b ¼ 24.7344 (12), c ¼ 13.3583 (7) Å,
b
¼ 91.399 (2)ꢁ, V ¼ 4351.8 (4)
Å3, D ¼ 1.179 g/cm3, T ¼ 223 (2) K,
l
¼ 0.71073 Å, Z ¼ 4,
Rint
¼
0.0346, 39602 reflections, 8263 independent, R1(all
data) ¼ 0.0463, wR2 ¼ 0.0821, GOF ¼ 1.036, CCDC-1529977.
Acknowledgements
(107 mg, 24%). 1H NMR (C6D6):
d
ꢀ1.81 (2H, s), ꢀ0.48 (2H, s), 1.17
(18H, “t”, 3 Hz), 1.30 (6H, br s), 1.36 (6H, br s). 13C NMR (C6D6):
The authors thank the US National Science Foundation (CHE-
1402149) and Cornell University for financial support.
d
ꢀ6.98, 14.51, 16.66, 26.54. 31P NMR (C6D6, 31P coupling constants
determined through spin simulation program MesReNova):
d
ꢀ19.58, 30.06 (AA' ¼ 27 Hz; XX' ¼ 24 Hz, AX ¼ A'X' ¼ 61 Hz). Anal.
Appendix A. Supplementary data
for C12H34FeP4 (calc.) C 40.24, H 9.57; (found) C 40.45, H 9.06.
Supplementary data related to this article can be found at http://
5.2.8. cis,trans-(PMe3)2Fe(k-C,P-CH2C6H4-o-PMe2)2 (6)
A 60 mL bomb reactor was charged with CH3C6H4-o-PMe2
(250 mg, 1.63 mmol) and 15 mL benzene. A separate vial was
charged with cis-Me2Fe(PMe3)4 (319 mg, 0.817 mmol) and 3 mL
benzene, and the it was added to the bomb, resulting in an orange
solution. The solution was stirred for 1 d at 23 ꢁC, followed by
heating to 55 ꢁC for 3 h. The volatiles were removed, and the solid
residue was taken up in pentane/benzene and transferred to a
References
j.jorganchem.2017.04.001
Jacobs, Brian P.
